Process for hydroprocessing heavy oils utilizing sepiolite-based catalysts

ABSTRACT

Disclosed is a catalyst and process for making same wherein sepiolite is ion exchanged with a Group Ib, IIb, IIb, IVb, Vb, or VIIa metal, impregnated with a VIa metal and exchanged with a magnesium salt with intervening processing steps of calcining. The catalyst composition is useful in removing metals and hydroprocessing of hydrocarbon feedstocks. The catalyst can also be mixed with a high silica/alumina ratio zeolite such as sodium ZSM-5 zeolite.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. Ser. No. 402,400,filed July 27, 1982, now U.S. Pat. No. 4,469,807.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to techniques for making hydrotreating catalystsfrom sepiolite. This invention further relates to processes forhydrotreating or selectively demetallizing hydrocarbons and thehydroprocessing of heavy oils.

2. Description of the Prior Art

The presence of impurities such as sulfur, nitrogen and metals in thehydrocarbon feedstocks now utilized in the manufacture of hydrocarbonfuels such as gasoline and diesel fuel is becoming increasinglyimportant. These feedstocks include crude oils, heavy oils, crackedoils, deasphalted oils, residual oils, vacuum gas oils, vacuum residue,oil from tar sands, shale and mixtures thereof. Sulfur, nitrogen andmetal impurities are discharged into the atmosphere, together with theexhaust gas when these hydrocarbons are burned and are thus anincreasing source of environmental pollution. The metals present in thefeedstocks are deposited on catalysts utilized in the catalytic crackingand/or hydroprocessing of hydrocarbons. These deposits cause a markeddecrease in the catalytic activity of the catalysts and theirselectivity. U.S. Pat. Nos. 4,152,250 and 4,196,102 describe thedemetallization of hydrocarbon feedstocks as well as theirdenitrification and desulfurization utilizing a catalyst which comprisesone or more metals selected from the group consisting of transitionmetals and metals of Group IIb of the periodic table supported onsepiolite carrier. U.S. Pat. No. 4,196,102 discloses a catalystcomprising one or more metals selected from the group consisting oftransition metals and metals of Group IIb of the Periodic Tablesupported on a sepiolite carrier to be useful in the demetallization ofhydrocarbons. We have now discovered that, in sepiolite-based catalysts,the residual acidity (both the indiginous acidity and that created inthe catalyst preparation steps) can be controlled if the exchangedcatalyst is subsequently is ion-exchanged with magnesium ions. Thecatalyst is further improved by incorporating with it, after themagnesium ion-exchanged, a high silica/alumina ratio zeolite to obtainthe desired type of acidity at the desired level.

SUMMARY OF THE INVENTION

This invention is directed to a process for making an improvedsepiolite-based hydroprocessing catalyst by controlling and modifyingthe acidity of the catalyst. The process comprises treating the catalystto effect back-exchange of magnesium ions for acidity control,optionally followed by mixing with low acidity zeolites. Initiallynatural or synthetic sepiolite is contacted with an aqueous solution ofthe salt of a metal such as cobalt to form a metal-exchanged sepioliteproduct. Subsequently the dried powdered product is contacted with anaqueous solution of a molybdenum compound and finally is contacted orion-exchanged with an aqueous magnesium salt solution to effection-exchange of magnesium ions. The magnesium effectively reduces theacidity of the sepiolite by neutrallizing the acid sites on thesepiolite. These acid sites are undesirable in hydroprocessing heavyresidua. We have also discovered that this catalyst composition whenadmixed in pulverized form with a zeolite of the ZSM-5 type having ahigh silica/alumina mole ratio, (greater than 10) results in an enhancedhydroprocessing catalyst. A sodium-exchanged zeolite is preferred. Instill another aspect this invention comprises the catalyst compositionmade by the aforedescribed procedures.

DETAILED DESCRIPTION OF THE INVENTION

Sepiolite is a porous, magnesium-silicate mineral similar to meerschaum.The sepiolite has the formula 2MgO.3SiO₂.4H₂ O (Hackh's ChemicalDictionary, Fourth Edition, McGraw Hill Book Company, 1969). It occursnaturally as an alteration product of serpentine or magnesite. Asynthetic counterpart can be prepared from cheaply available siliciccompounds and magnesium salt and is marketed in the trade as magnesiumtrisilicate. For the purpose of the present invention any natural orsynthetic sepiolite can be employed and both the alpha-type sepioliteand beta-type sepiolite that are known to exist can be used in thepresent invention.

The catalytic metal or metals to be supported on the sepiolite accordingto the present invention, are one or more of metals selected from thegroup consisting of metals of Group Ib and transition metals of theperiodic table. Namely, use is made of one or more of compounds ofelements selected from the group consisting of the compounds of Cu, Agand Au of Group Ib; Sc, Y, lanthanides and actinides of Group IIIb; Ti,Zr and Hf of Group IVb; V, Nb and Ta of Group Vb; Cu, Mo and W of GroupVIa; Mn, Tc and Re of Group VIIa; and Fe, Co and Ni of iron group, Ru,Rh and Pd of palladium group, Os, Ir and Pt of platinum group; and Zn,Cd and Hg of Group IIb. Among these metals the preferable are Co, Ni,Fe, Cu, lanthanides, V, Cr, Mo and W. Furthermore, the combined use ofboth one or more compounds of the metal(s) selected from Co, Ni, Fe, Cu,and lanthanides, and one or more compounds of metal(s) selected from Mo,W and V is especially effective in the present invention.

These metals are generally utilized in the forms of salts, e.g.,nitrates, sulfates, salts of metallic acids, complex salts, or otherwater-soluble compounds. The addition of these compounds to sepiolitecan be conducted according to conventional methods such as immersion,spraying and kneading as described in U.S. Pat. No. 4,196,102 which isincorporated herein by reference. For cobalt, nickel, iron, copper, etc.the preferred method is ion-exchange. For molybdenum, tungsten,vanadium, etc. the preferred method is impregnation. These compounds areemployed generally in an amount of 1% to 15% by weight (as metal) on thebasis of carrier (as anhydride), and usually 2% to 13% by weight ispreferred.

To prepare the improved catalyst of this invention, sepiolite is firstpulverized, if necessary, to a particle size of less than 100 mesh andis dried at a temperature of about 120° C. for approximately 2 hours andallowed to cool. The cooled dried clay is then mixed with approximately4 times its volume of an aqueous solution containing a concentration ofa first metal salt for ion-exchange that will give the desired ultimatepercent of metal in the catalyst, preferably between 1 and 4 percent.The preferred method of metal incorporation is by ion-exchange.Preferred metals which can be used include cobalt, iron and nickel. Whencobalt is the chosen metal, the cobalt salt is introduced by the use ofan acid solution of cobalt of a pH of 1 to 3 that has the property ofion exchange, for the magnesium present in the sepiolite. The acidity ofthis ion-exchanged solution also affects ion-exchange for magnesium ionsin the sepiolite creating an undesirable acidity of the sepiolite. Themost preferred metal is cobalt. The sepiolite is separated from theaqueous solution and is washed with water, at a ratio of 2 volumes ofwater to 1 of sepiolite. The washed metal-exchanged sepiolite is thendried at approximately 120° C. for approximately 2-3 hours and iscalcined then at 500° C. for 2-4 hours.

The calcined, metal-exchanged sepiolite is then pulverized, and thepulverized material is mixed with an aqueous solution containing therequired amount of a salt containing the second metal such as ammoniummeta-molybdate. This solution is maintained at a pH of 10-12 withammonium hydroxide and in sufficient concentration to provide aconcentration in the final catalyst of 8-15 percent by weight ofmolybdenum. The ammonium ion in this solution is also ion-exchanged withmagnesium and hydrogen ions in the sepiolite to form ammonium salts fromwhich undesirable acidity is created when the salts later are calcined.The thus treated sepiolite is then separated from the aqueous solutionand is dried at 120° C. for 2 hours and calcined at approximately 500°C. for 2-4 hours.

In a third step, the calcined metal-exchanged/impregnated sepiolite isthen pulverized and saturated with an aqueous solution of magnesium saltmaintained at a pH of approximately 6.5 to 7 by the addition of asoluble magnesium compound, to effect ion-exchange between acidity ofthe sepiolite and magnesium ions, such as magnesium acetate. Theconcentration of magnesium in the final product is between 18 and 25percent by weight. This ion-exchange is necessary to eliminate theundersirable residual acidity of the sepiolite catalyst carrier whichwas generated in the first metal exchange step carried out in acidsolution and the ammonium ion exchange in the second step. The solid isthen separated, dried at 120° C. for 2 hours and calcined at 500° C. for2-4 hours.

As noted previously, the catalyst thus formed can be admixed with a highsilica/alumina ratio zeolite such as sodium ZSM-5. We have discoveredthat this low acidity, high silica/alumina ratio zeolite provides thedesirable and necessary acidity required for catalytic reactions. Theacidity of this zeolite can be controlled by ion-exchange withpotassium, or sodium. The desirable acidity as expressed by an alphavalue is less than 10, and preferably less than 1. As is known in theart, the alpha value is an approximate indication of the catalyticcracking activity of the catalyst compared to a standard catalyst and itgives the relative rate constant (rate of normal hexane conversion pervolume of catalyst per unit times). It is based on the activity of thishighly active silica/alumina cracking catalyst taken as an alpha of 1(rate constant=0.016). The alpha test is described in U.S. Pat. No.3,354,078 and in the Journal of Catalysis, Vol. IV, pp. 522-529 (August,1965) both of which are incorporated herein by reference. These zeolitesmay be described as ones wherein the silica/alumina mole ratio rangesupwardly from 10. The two catalysts in admixture are pulverized to theappropriate particle size for use in a catalyst bed. The ratio by weightof sepiolite catalyst to the high silica/alumina ratio zeolitepreferably is between 2 and 100. Sodium-exchanged zeolites of the ZSM-5type are preferred. Representative of the ZSM-5 type zeolites are ZSM-5,ZSM-11, ZSM-23, ZSM-35 and ZSM-38. ZSM-5 is disclosed and claimed inU.S. Pat. No. 3,702,886 and U.S. Pat. No. Re. 29,948; ZSM-11 isdisclosed and claimed in U.S. Pat. No. 3,709,979. Also, see U.S. Pat.No. 3,832,449 for ZSM-12; U.S. Pat. No. 4,076,842 for ZSM-23; U.S. Pat.No. 4,016,245 fort ZSM-35 and U.S. Pat. No. 4,406,839 for ZSM-38. Thedisclosures of these patents are incorporated herein by reference.

The catalyst of the present invention can be employed in a wide varietyof hydrotreating reactions for a wide range of hydrocarbons. Thecatalyst is particularly useful for desulfurization, denitrification anddemetallation of heavy oils. In these processes the feedstock and thecatalyst should be contacted at a temperature between 350° C. and 450°C., a hydrogen pressure of between 500 and 1000 psig, and an LHSV of 0.1to 10.

EXAMPLE 1

A sepiolite catalyst containing 2.5% by weight of cobalt and 12% byweight of molybdenum, and fully saturated with magnesium was preparedaccording to the process described herein.

EXAMPLE 2

A sepiolite catalyst composition was prepared containing 2.5% by weightof cobalt and 12.% by weight of molybdenum following the proceduredescribed in U.S. Pat. No. 4,152,250.

EXAMPLE 3

A third sepiolite catalyst composition was prepared by mixing 9 parts ofthe catalyst prepared in Example 1 with 1 part of a sodium-exchangedzeolite NaZSM-5 having a silica/alumina ratio of 26,000 to 1.

EXAMPLE 4

In separate runs, a 16 cc sample of each of the catalysts prepared asdescribed above was packed in a reactor, and the reactor was placed in athree-zone, thermostatically-controlled furnace. The reactor was thensulfided at 375° C. using 1% hydrogen sulfide in a hydrogen carrieruntil the gas exiting the reactor turned moist lead acetate paper black.This indicated that all the cobalt and molybdenum in the catalyst hadreacted with the H₂ S.

The reactor containing the sulfided catalyst was then connected to ahydrogen source and the system was pressurized to a desired pressure,usually 1500 psig, with hydrogen. When the required pressure andtemperature were reached, hydrogen flow was adjusted such as theequivalent of 6,000-8,000 standard cubic feet of hydrogen/barrel of feedto be processed would flow over the catalyst. When the correct pressure,temperature and amount of hydrogen gas were adjusted, the appropriateamount of a feedstock of an API gravity of 2.8 containing 5.77% byweight of sulfur and 58 ppm nickel and 186 ppm of vanadium was flowedover the catalyst. Samples were then taken from the product at regularintervals, and analyzed. Table 1 shows the data obtained from thisanalysis and demonstrates the effectiveness of the composition of thisinvention (Examples 1 and 3) over the prior art catalyst of Example 2.

                  TABLE 1                                                         ______________________________________                                        Desulfurization/Demetallation of Arab Heavy Vacuum Residue at                 1500 psig, 0.25 LHSV and 6000-8000 SCF/bbl Using the Different                Catalysts at 400° C. at 42 Volumes per Volume of Catalyst              CONCENTRATION BY                                                              WEIGHT IN TREATED PRODUCT                                                     Sulfur           Nickel       Vanadium                                                    % Re-           % Re-        % Re-                                Wt %        moved    PPM    moved   PPM  moved                                ______________________________________                                        Feedstock                                                                             5.77    --       58   --      186  --                                 Example 1                                                                             2.3     (60)     25   (53)    26   (86)                               Example 2                                                                             2.9     (49)     37   (30)    69   (62)                               Example 3                                                                             1.9     (67)     17   (69)    18   (90)                               ______________________________________                                    

The data in Table 1 is significant in that the reduction in sulfur,nickel and vanadium in the resid treated with catalyst made according toExample 1 demonstrate that treating a catalyst with magnesium asdisclosed herein substantially improves the ability of the catalyst toremove sulfur, nickel and vanadium from a heavy oil. Example 2illustrates the limited abilities of the prior art catalyst compositionswherein no magnesium treatment has been performed. Example 3demonstrates the additional improvement in the ability of the catalystto remove nickel, sulfur, and vanadium when the catalyst is combinedwith a sodium exchanged zeolite.

This invention is particularly noteworthy in that it provides a methodof controlling the acidity of a sepiolite based, based-exchangedcatalyst by providing a means of neutralizing the acid sites withmagnesium ions. The invention is further noteworthy in that it providesa method for closely controlling the acidity of a catalyst mixture byincorporating a sodium exchanged zeolite having a high silica/aluminaratio.

What is claimed is
 1. A process for demetallizing and desulfurizing ahydrocarbon oil comprising contacting said hydrocarbon oil in thepresence of hydrogen and a sepiolite-based catalyst composition underconditions of pressure and temperature sufficient to effectdemetallization and desulfurization, said sepiolite-based catalystcomposition having been prepared by first contacting said sepiolite withan aqueous solution of a first metal salt, then contacting the resultantmetal ion-exchanged sepiolite with an aqueous solution of a compound ofa second metal selected from the group consisting of molybdyenum,tungsten and vanadium, and finally contacting the resultantmetal-exchanged sepiolite product with an aqueous solution of amagnesium compound, thereby effecting a magnesium ion-exchange with themetal-exchanged sepiolite product and neutralizing acid sites on saidsepiolite product.
 2. The process of claim 1 wherein said first metalsalt is a salt of a metal selected from the group consisting of iron,cobalt and nickel.
 3. The process of claim 1 wherein said first metalsalt is a cobalt salt.
 4. The process of claim 1 wherein said secondmetal is molybdenum.
 5. The process of claim 1 wherein the concentrationof said first metal in elemental form in the catalyst product is betweenabout 1 and about 4 percent by weight and the concentration of saidsecond metal in elemental form is between about 8 and about 15 percentby weight.
 6. The process of claim 1 wherein the concentration of addedmagnesium in the resultant catalyst product is between 18 and 25 percentby weight.
 7. The process of claim 1 wherein said sepiolite catalyst ismixed with a high silica/alumina mole ratio zeolite.
 8. The process ofclaim 7 wherein the ratio by weight of metal-exchanged sepiolite tozeolite is between about 2 and about 100 in the resultant mixture. 9.The process of claim 7 wherein the mole ratio of silica to alumina insaid zeolite is greater than
 10. 10. The process of claim 7 wherein thezeolite in said mixture is a zeolite selected from the group consistingof ZSM-5, ZSM-11, ZSM-23, ZSM-35 and ZSM-38.
 11. The process of claim 7wherein the zeolite in said mixture is ZSM-5 zeolite.
 12. The process ofclaim 7 wherein said zeolite is a sodium-exchanged zeolite.
 13. Aprocess for demetallizing and desulfurizing a hydrocarbon oil comprisingcontacting said hydrocarbon oil in the presence of hydrogen and asepiolite-based catalyst composition at a hydrogen pressure of betweenabout 500 and abouat 100 psig, a temperature of between abut 350° C. and450° C. and a LHSV of between 0.1 and 10, said sepiolite-based catalystcomposition having been prepared by first contacting said sepiolite withan aqueous solution of a first metal salt, then contacting the resultantmetal ion-exchanged sepiolite with an aqueous solution of a compound ofa second metal selected from the group consisting of molybdenum,tungsten and vanadium, and finally contacting the resultantmetal-exchanged sepiolite product with an aqueous solution of amagnesium compound, thereby effecting a magnesium ion-exchange with themetal-exchanged sepiolite product and neutralizing acid sites on saidsepiolite product.
 14. The process of claim 13 wherein said first metalsalt is a salt of a metal selected from the group consisting of iron,cobalt and nickel.
 15. The process of claim 13 wherein said first metalsalt is a cobalt salt.
 16. The process of claim 13 wherein said secondmetal is molybdenum.
 17. The process of claim 13 wherein theconcentration of said first metal in elemental form in the catalystproduct is between about 1 and about 4 percent by weight and theconcentration of said second metal in elemental form is between about 8and about 15 percent by weight.
 18. The process of claim 13 wherein theconcentration of added magnesium in the resultant catalyst product isbetween 18 and 25 percent by weight.
 19. The process of claim 13 whereinsaid sepiolite catalyst is mixed with a high silica/alumina mole ratiozeolite.
 20. The process of claim 19 wherein the ratio by weight ofmetal-exchanged sepiolite to zeolite is between about 2 and about 100 inthe resultant mixture.
 21. The process of claim 19 wherein the moleratio of silica to alumina in said zeolite is greater than
 10. 22. Theprocess of claim 19 wherein the zeolite in said mixture is a zeoliteselected from the group consisting of ZSM-5, ZSM-11, ZSM-23, ZSM-35 andZSM-38.
 23. The process of claim 19 wherein the zeolite in said mixtureis ZSM-5 zeolite.
 24. The process of claim 19 wherein said zeolite is asodium-exchanged zeolite.